Herbicidal ortho-(azinyl)-benzenesulfonamides

ABSTRACT

This invention relates to novel ortho-(azinyl)benzenesulfonamides, such as N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-(2-pyridinyl)benzene-sulfonamide, and their use as pre-emergent or post-emergent herbicides or plant growth regulants.

BACKGROUND OF THE INVENTION

The present invention relates to ortho-heterocyclic benzenesulfonylureas and, more particularly, to ortho-(mono, di or triazinyl)benzenesulfonylureas and to their use as pre- or post-emergent herbicides or as plant growth regulants.

U.S. patent application Ser. No. 337,932, filed Jan. 7, 1982, now matured into U.S. Pat. No. 4,465,505 issued Aug. 14, 1984 discloses and claims ortho-heterocyclic benzenesulfonylureas which are useful as herbicides or plant growth regulants. Compounds taught therein have the following general structure ##STR1## wherein Q can be, among other values, ##STR2## W can be O, S or NR; the R substituents can be, with a few exceptions, H, lower alkyl or lower alkoxy;

X and Y can be CH₃ or OCH₃ ; and

Z can be CH or N.

U.S. patent application Ser. No. 337,934, filed Jan. 7, 1982, now abandoned relates to ortho-heterocyclicbenzenesulfonamides, such as ##STR3## Z can be CH or N which are useful as general and selective herbicides and as plant growth regulants.

U.S. patent application Ser. No. 337,933, filed Jan. 7, 1982, now matured into U.S. Pat. No. 4,460,401 issued July 17, 1984 also relates to ortho-heterocyclicbenzenesulfonylureas, in particular, ortho-furanylbenzenesulfonylureas, ortho-thienylbenzenesulfonylureas and ortho-pyrrolylbenzenesulfonylureas, and to their use as herbicides and plant growth regulants.

SUMMARY OF THE INVENTION

The present invention relates to compounds of Formula I, to suitable agricultural compositions containing them as an active ingredient and to their use as pre-emergent or post-emergent herbicides or plant growth regulants. ##STR4## R₁ is H, F, Cl, CH₃ or OCH₃ ; R₂, R₃, R₅, R₉, R₁₀, R₁₁, R₁₂ and R₁₇ are independently H or CH₃ ;

R₇, R₈, R₄ and R₆ are independently H, CH₃ or OCH₃ ;

R₁₃, R₁₄, R₁₅ and R₁₆ are independently CH₃ or OCH₃ ;

X is CH₃, OCH₃ or Cl;

Y is CH₃, C₂ H₅, CH₂ OCH₃, OCH₃, OC₂ H₅, CH(OCH₃)₂ NH₂, NHCH₃ or N(CH₃)₂ ;

Z is CH or N

provided that when X is Cl, then Z is CH and Y is OCH₃, OC₂ H₅, NH₂, NHCH₃ or N(CH₃)₂ and when R₁ is CH₃, it is in the 3-, 4- or 5-position of the benzene ring;

and their agriculturally suitable salts.

Preferred for reasons of their higher herbicidal activity and/or more favorable ease of synthesis are:

(1) Compounds of Formula I where R₁ and R₁₇ are H.

(2) Compounds of Preferred (1) where Y is CH₃, OCH₃, CH₂ OCH₃ or N(CH₃)₂.

(3) Compounds of Preferred (2) where Q is ##STR5## (4) Compounds of Preferred (2) where Q is ##STR6## (5) Compounds of Preferred (2) where ##STR7## (6) Compounds of Preferred (2) where ##STR8## (7) Compounds of Preferred (2) where ##STR9## (8) Compounds of Preferred (2) where ##STR10##

Specifically preferred for reasons of their highest herbicidal activity and/or most favorable ease of synthesis are:

N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-(2-pyridinyl)benzenesulfonamide;

N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-(2-pyridinyl)benzenesulfonamide;

N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-pyridinyl)benzenesulfonamide; and

N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-(2-pyrimidinyl)benzenesulfonamide.

DETAILED DESCRIPTION OF THE INVENTION Synthesis

The ortho-heterocyclicbenzenesulfonylureas of Formula I can be prepared by reacting the appropriately substituted benzenesulfonamide with an appropriate methyl pyrimidinyl carbamate or methyl triazinyl carbamate in the presence of an equimolar amount of trimethylaluminum according to the procedure of Equation 1. Unless indicated otherwise, all temperatures are in °C. ##STR11## wherein R₁, R₁₇, Q, X, Y, and Z are as previously defined.

The reaction of Equation 1 is best carried out in methylene chloride at 25° to 40° C. for 24 to 96 hours under a nitrogen atmosphere. The product can be isolated by the addition of an aqueous acetic acid solution followed by extraction of the product into methylene chloride or direct filtration of a product of low solubility. The product can ordinarily be purified by trituration with solvents such as n-butyl chloride or ether or by column chromatography.

Further details of this reaction and the preparation of the carbamates of Formula III can be found in U.S. Ser. No. 337,934.

Sulfonamides of Formula II may be prepared by the sequence of reactions outlined in Equation 2. ##STR12## wherein R₁ and Q are as previously defined.

The compounds of Formula V are prepared by analogy with the teaching of J. G. Lombardino in J. Org. Chem., 36, 1843.

An N-t-butyl sulfonamide of Formula IV is dissolved in an ethereal solvent, such as tetrahydrofuran, and two equivalents of n-butyllithium in hexane are added at 0°-25°. After 1-5 hours at 0°-25°, the compound of Formula V is formed. This is not isolated, but one equivalent of a copper (I) salt is added at -20° to 0°, followed by 1-1.5 equivalents of an appropriately substituted heteroaromatic iodide (VI). The reaction mixture is then heated at 40°-70° for 1-3 days, concentrated, poured onto aqueous ammonia, and filtered to provide the compound of Formula VII. The reaction of Formula 2c is conducted by heating a compound of Formula VII with 2-10 equivalents of trifluoroacetic acid or aqueous HBr with or without an inert solvent at 30°-70° for 1-3 days. The product II may be isolated as a trifluoroacetate or hydrobromide salt by evaporation of solvent and excess acid and trituration with ether. The free base may be obtained by neutralization of the salt with aqueous base, extraction into an organic solvent, and concentration of the organic extracts.

The compounds of Formula VI may be prepared according to the methods known in the art, such as those reviewed in "The Chemistry of Heterocyclic Compounds," a series published by Interscience Publ., New York and London, the teachings of which are incorporated herein by reference. The iodopyridines are described in Vol. 14 of the above series, pp. 407-488. Iodopyrimidines are described by D. J. Brown and S. F. Mason in Vol. 16 of the above series. The preparation of iodopyrazines is taught by A. Hirschberg and P. E. Spoerri, J. Org. Chem., 26, 1907 (1981) and iodopyridazines are described by D. L. Aldons and R. N. Castle in Vol. 28 of the Interscience series, pp. 240-241. The iodo-1,3,5-triazines are described by E. M. Smolin and L. Rapoport, in Vol. 13 of the above series, and a method for preparing iodo-1,2,4-triazines is taught by A. Rykowski and H. C. van der Plas, in J. Org. Chem., 45, 881 (1980).

The present invention is further illustrated, in part, by the following examples.

EXAMPLE 1 N-(1,1-dimethylethyl)-2-(2-pyridinyl)benzenesulfonamide

To a solution of 30 g of N-(1,1-dimethylethyl)-2-(2-pyridinyl)benzenesulfonamide in 600 ml of tetrahydrofuran was added 190 ml of 1.6M butyllithium in hexane at -10° to 10°. The reaction mixture was allowed to stir at 25° for 1 hour, then cooled to -10° and 28 g of cuprous iodide was added. After 15 minutes stirring at 0°, 35 g of 2-iodopyridine was added and the mixture was heated to reflux for 16 hours. After cooling to 25°, 25 ml of acetic acid was added and solvent was removed in vacuo. A cold solution of aqueous ammonia was added and the precipitate was filtered. The solid was digested with methylene chloride and filtered. The filtrate was concentrated, triturated with n-chlorobutane, and the solid was filtered to afford 36 g (78%) of product, m.p. 147°-150°. NMR(CDCl₃)δ: 1.3 (s, 9), 7.1-8.7 (m, 9).

EXAMPLE 2 2-(2-pyridinyl)benzenesulfonamide

A solution of 14.8 g of the sulfonamide from Example 1 and 10 ml of 48% hydrobromic acid in 100 ml of methanol was heated at 40°-45° for 16 hours, concentrated, and neutralized wth aqueous sodium bicarbonate. The solid was filtered, washed with ice-water, and air-dried to afford 6.0 g of product, m.p. 186°-190°. NMR(CDCl₃ /DMSO-d₆)δ: 7.5 (m, 7), 8.1 (m, 2), 8.6 (d, 1). 1R(Nujol) 3300, 3260 cm⁻¹. m/e M⁺ 234.

EXAMPLE 3 N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-pyridinyl)benzenesulfonamide

A solution of 1.2 g of the compound from Example 2 and 1.3 g of methyl N-(4,6-dimethoxypyrimidin-2-yl)-carbamate in 50 ml of methylene chloride was stirred under nitrogen and 3.4 ml of a 2N solution of trimethylaluminum in toluene was added. After heating at reflux for 4 days, the solution was cooled to 0°, 3 ml of 2N HCl (aq.) was added, the mixture was partitioned between methylene chloride and water. The organic layer was concentrated and the residue was chromatographed on silica gel to afford 0.9 g of the product, m.p. 175°-176°. NMR (DMSO-d₆)δ: 3.8 (s, 6), 6.0 (s, 1), 7.2-8.3 (m).

m/e (M⁺ +1) 416. IR 1700 cm⁻¹.

Using the procedures described in the equations and Examples 1-3 above, the compounds described in the following Tables I-X can be prepared.

                                      TABLE I                                      __________________________________________________________________________      ##STR13##                                                                     R.sub.1                                                                             R.sub.2                                                                            R.sub.3                                                                            R.sub.17                                                                           X   Y      Z   m.p. (°C.)                              __________________________________________________________________________     H    H   H   H   CH.sub.3                                                                           CH.sub.3                                                                              CH  171-174°                                H    H   H   H   CH.sub.3                                                                           OCH.sub.3                                                                             CH  180-184°                                H    H   H   H   OCH.sub.3                                                                          OCH.sub.3                                                                             CH  175-176°                                H    H   H   H   CH.sub.3                                                                           CH.sub.3                                                                              N                                                  H    H   H   H   CH.sub.3                                                                           OCH.sub.3                                                                             N   160-173°                                H    H   H   H   OCH.sub.3                                                                          OCH.sub.3                                                                             N   172-205°                                H    H   H   H   CH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                    CH                                                 H    H   H   H   CH.sub.3                                                                           CH(OCH.sub.3).sub.2                                                                   CH                                                 H    H   H   H   OCH.sub.3                                                                          N(CH.sub.3).sub.2                                                                     N                                                  H    H   H   H   OCH.sub.3                                                                          NH.sub.2                                                                              CH                                                 H    H   H   H   Cl  OCH.sub.3                                                                             CH                                                 H    H   H   H   OCH.sub.3                                                                          NHCH.sub.3                                                                            CH                                                 H    H   H   H   CH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                    N                                                  H    H   H   H   Cl  CH.sub.3                                                                              CH                                                 H    H   H   H   OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                                                   N                                                  H    4'-CH.sub.3                                                                        H   H   CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 H    4'-CH.sub.3                                                                        6'CH.sub.3                                                                         H   CH.sub.3                                                                           OCH.sub.3                                                                             CH                                                 H    5'-CH.sub.3                                                                        H   H   OCH.sub.3                                                                          OCH.sub.3                                                                             N                                                  H    3'-CH.sub.3                                                                        H   H   OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                 H    3'-CH.sub.3                                                                        5'-CH.sub.3                                                                        H   CH.sub.3                                                                           OCH.sub.3                                                                             CH                                                 H    6'-CH.sub.3                                                                        H   H   OCH.sub.3                                                                          CH.sub.3                                                                              N                                                  H    H   H   CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 H    H   H   CH.sub.3                                                                           OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                 H    6'-CH.sub. 3                                                                       H   H   CH.sub.3                                                                           CH.sub.3                                                                              N                                                  H    4'-CH.sub.3                                                                        H   H   OCH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                    N                                                  H    5'-CH.sub.3                                                                        H   H   CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 H    H   H   H   OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                                                   CH                                                 3-F  H   H   H   CH.sub.3                                                                           CH.sub.3                                                                              N                                                  3-F  H   H   H   OCH.sub.3                                                                          CH.sub.3                                                                              N                                                  3-F  H   H   H   CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                     CH                                                 3-F  H   H   H   Cl  OCH.sub.3                                                                             CH                                                 3-F  H   H   CH.sub.3                                                                           OCH.sub.3                                                                          NH.sub.2                                                                              N                                                  3-F  H   H   H   CH.sub.3                                                                           OCH.sub.3                                                                             N                                                  4-Cl H   H   H   OCH.sub.3                                                                          CH.sub.3                                                                              CH                                                 4-Cl H   H   H   CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                      CH                                                 4-Cl H   H   H   OCH.sub.3                                                                          C.sub.2 H.sub.5                                                                       N                                                  4-Cl 6'-CH.sub.3                                                                        H   H   Cl  CH.sub.2 OCH.sub.3                                                                    N                                                  4-Cl H   H   H   OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                 4-Cl H   H   CH.sub.3                                                                           CH.sub.3                                                                           OCH.sub.3                                                                             CH                                                 5-CH.sub.3                                                                          H   H   H   OCH.sub.3                                                                          NHCH.sub.3                                                                            N                                                  5-CH.sub.3                                                                          H   H   H   CH.sub.3                                                                           C.sub.2 H.sub.5                                                                       N                                                  5-CH.sub.3                                                                          H   H   H   OCH.sub.3                                                                          CH.sub.3                                                                              CH                                                 5-CH.sub.3                                                                          H   H   H   CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 5-CH.sub.3                                                                          H   H   H   OCH.sub.3                                                                          CH.sub.3                                                                              N                                                  4-OCH.sub.3                                                                         H   H   H   CH.sub.3                                                                           OCH.sub.3                                                                             N                                                  4-OCH.sub.3                                                                         H   H   H   OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                 4-OCH.sub.3                                                                         H   H   H   CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 4-OCH.sub.3                                                                         H   H   H   OCH.sub.3                                                                          OCH.sub.3                                                                             N                                                  __________________________________________________________________________

                                      TABLE II                                     __________________________________________________________________________      ##STR14##                                                                     R.sub.1                                                                             R.sub.2                                                                            R.sub.3                                                                            R.sub.17                                                                           X   Y      Z   m.p. (°C.)                              __________________________________________________________________________     H    H   H   H   CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 H    H   H   H   CH.sub.3                                                                           OCH.sub.3                                                                             CH                                                 H    H   H   H   OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                 H    H   H   H   CH.sub.3                                                                           CH.sub.3                                                                              N                                                  H    H   H   H   CH.sub.3                                                                           OCH.sub.3                                                                             N                                                  H    H   H   H   OCH.sub.3                                                                          OCH.sub.3                                                                             N                                                  H    H   H   H   CH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                    CH                                                 H    H   H   H   CH.sub.3                                                                           CH(OCH.sub.3).sub.2                                                                   CH                                                 H    H   H   H   OCH.sub.3                                                                          N(CH.sub.3).sub.2                                                                     N                                                  H    H   H   H   OCH.sub.3                                                                          NH.sub.2                                                                              CH                                                 H    H   H   H   Cl  OCH.sub.3                                                                             CH                                                 H    H   H   H   OCH.sub.3                                                                          NHCH.sub.3                                                                            CH                                                 H    H   H   H   CH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                    N                                                  H    H   H   H   Cl  CH.sub.3                                                                              CH                                                 H    H   H   H   OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                                                   N                                                  H    2'-CH.sub.3                                                                        H   H   OCH.sub.3                                                                          CH.sub.3                                                                              CH                                                 H    5'-CH.sub.3                                                                        6'-CH.sub.3                                                                        H   OCH.sub.3                                                                          CH.sub.3                                                                              N                                                  H    6'-CH.sub.3                                                                        H   H   CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 H    5'-CH.sub.3                                                                        H   H   CH.sub.3                                                                           OCH.sub.3                                                                             CH                                                 H    4'-CH.sub.3                                                                        6'-CH.sub.3                                                                        H   OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                 H    2'-CH.sub.3                                                                        H   H   OCH.sub.3                                                                          OCH.sub.3                                                                             N                                                  H    H   H   CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 H    H   H   CH.sub.3                                                                           OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                 H    6'-CH.sub.3                                                                        H   H   CH.sub.3                                                                           CH.sub.3                                                                              N                                                  H    H   H   H   OCH.sub.3                                                                          CH.sub.2 OCH.sub. 3                                                                   N                                                  H    4'-CH.sub.3                                                                        H   H   CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 H    H   H   H   OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                                                   CH                                                 6-F  H   H   H   CH.sub.3                                                                           CH.sub.3                                                                              N                                                  6-F  H   H   H   OCH.sub.3                                                                          CH.sub.3                                                                              N                                                  6-F  H   H   H   CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                     CH                                                 6-F  H   H   H   Cl  OCH.sub.3                                                                             CH                                                 6-F  H   H   CH.sub.3                                                                           OCH.sub.3                                                                          NH.sub.2                                                                              N                                                  6-F  H   H   H   CH.sub.3                                                                           OCH.sub.3                                                                             N                                                  3-Cl H   H   H   OCH.sub.3                                                                          CH.sub.3                                                                              CH                                                 3-Cl H   H   H   CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                      CH                                                 3-Cl H   H   H   OCH.sub.3                                                                          C.sub.2 H.sub.5                                                                       N                                                  3-Cl H   H   H   Cl  CH.sub.2 OCH.sub.3                                                                    N                                                  3-Cl H   H   H   OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                 3-Cl H   H   CH.sub.3                                                                           CH.sub.3                                                                           OCH.sub.3                                                                             CH                                                 4-CH.sub.3                                                                          H   H   H   OCH.sub.3                                                                          NHCH.sub.3                                                                            N                                                  4-CH.sub.3                                                                          5'-CH.sub.3                                                                        H   H   CH.sub.3                                                                           C.sub.2 H.sub.5                                                                       N                                                  4-CH.sub.3                                                                          H   H   H   OCH.sub.3                                                                          CH.sub.3                                                                              CH                                                 4-CH.sub.3                                                                          H   H   H   CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 4-CH.sub.3                                                                          H   H   H   OCH.sub.3                                                                          CH.sub.3                                                                              N                                                  5-OCH.sub.3                                                                         H   H   H   CH.sub. 3                                                                          OCH.sub.3                                                                             N                                                  5-OCH.sub.3                                                                         H   H   H   OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                 5-OCH.sub.3                                                                         H   H   H   CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 5-OCH.sub.3                                                                         H   H   H   OCH.sub.3                                                                          OCH.sub.3                                                                             N                                                  __________________________________________________________________________

                                      TABLE III                                    __________________________________________________________________________      ##STR15##                                                                     R.sub.1                                                                             R.sub.2                                                                            R.sub.3                                                                            R.sub.17                                                                           X   Y      Z   m.p. (°C.)                              __________________________________________________________________________     H    H   H   H   CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 H    H   H   H   CH.sub.3                                                                           OCH.sub.3                                                                             CH                                                 H    H   H   H   OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                 H    H   H   H   CH.sub.3                                                                           CH.sub.3                                                                              N                                                  H    H   H   H   CH.sub.3                                                                           OCH.sub.3                                                                             N                                                  H    H   H   H   OCH.sub.3                                                                          OCH.sub.3                                                                             N                                                  H    H   H   H   CH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                    CH                                                 H    H   H   H   CH.sub.3                                                                           CH(OCH.sub.3).sub.2                                                                   CH                                                 H    H   H   H   OCH.sub.3                                                                          N(CH.sub.3).sub.2                                                                     N                                                  H    H   H   H   OCH.sub.3                                                                          NH.sub.2                                                                              CH                                                 H    H   H   H   Cl  OCH.sub.3                                                                             CH                                                 H    H   H   H   OCH.sub.3                                                                          NHCH.sub.3                                                                            CH                                                 H    H   H   H   CH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                    N                                                  H    H   H   H   Cl  CH.sub.3                                                                              CH                                                 H    H   H   H   OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                                                   N                                                  H    2'-CH.sub.3                                                                        H   H   CH.sub.3                                                                           OCH.sub.3                                                                             N                                                  H    2'-CH.sub.3                                                                        6'-CH.sub.3                                                                        H   CH.sub.3                                                                           OCH.sub.3                                                                             CH                                                 H    3'-CH.sub.3                                                                        H   H   CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 H    2'-CH.sub.3                                                                        H   H   OCH.sub.3                                                                          OCH.sub.3                                                                             N                                                  H    3'-CH.sub.3                                                                        6'-CH.sub.3                                                                        H   OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                 H    2'-CH.sub.3                                                                        H   H   CH.sub.3                                                                           OCH.sub.3                                                                             CH                                                 H    H   H   CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 H    H   H   CH.sub.3                                                                           OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                 H    2'-CH.sub.3                                                                        H   H   CH.sub.3                                                                           CH.sub.3                                                                              N                                                  H    H   H   H   OCH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                    N                                                  H    3'-CH.sub.3                                                                        H   H   CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 H    H   H   H   OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                                                   CH                                                 5-F  H   H   H   CH.sub.3                                                                           CH.sub.3                                                                              N                                                  5-F  H   H   H   OCH.sub.3                                                                          CH.sub.3                                                                              N                                                  5-F  H   H   H   CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                     CH                                                 5-F  H   H   H   Cl  OCH.sub.3                                                                             CH                                                 5-F  H   H   CH.sub.3                                                                           OCH.sub.3                                                                          NH.sub.2                                                                              N                                                  5-F  H   H   H   CH.sub.3                                                                           OCH.sub.3                                                                             N                                                  4-Cl H   H   H   OCH.sub.3                                                                          CH.sub.3                                                                              CH                                                 4-Cl H   H   H   CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                      CH                                                 4-Cl H   H   H   OCH.sub.3                                                                          C.sub.2 H.sub.5                                                                       N                                                  4-Cl H   H   H   Cl  CH.sub.2 OCH.sub.3                                                                    N                                                  4-Cl H   H   OCH.sub.3                                                                          OCH.sub.3                                                                          CH                                                        4-Cl 2'-CH.sub.3                                                                        6'-CH.sub.3                                                                        CH.sub.3                                                                           CH.sub.3                                                                           OCH.sub.3                                                                             CH                                                 3-CH.sub.3                                                                          H   H   H   OCH.sub.3                                                                          NHCH.sub.3                                                                            N                                                  3-CH.sub.3                                                                          H   H   H   CH.sub.3                                                                           C.sub.2 H.sub.5                                                                       N                                                  3-CH.sub.3                                                                          H   H   H   OCH.sub.3                                                                          CH.sub.3                                                                              CH                                                 3-CH.sub.3                                                                          H   H   H   CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 3-CH.sub.3                                                                          H   H   H   OCH.sub.3                                                                          CH.sub.3                                                                              N                                                  3-OCH.sub.3                                                                         H   H   H   CH.sub.3                                                                           OCH.sub.3                                                                             N                                                  3-OCH.sub.3                                                                         H   H   H   OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                 3-OCH.sub.3                                                                         H   H   H   CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 3-OCH.sub.3                                                                         H   H   H   OCH.sub.3                                                                          OCH.sub.3                                                                             N                                                  __________________________________________________________________________

                                      TABLE IV                                     __________________________________________________________________________      ##STR16##                                                                     R.sub.1                                                                             R.sub.4                                                                            R.sub.5                                                                           R.sub.6                                                                            R.sub.17                                                                          X   Y      Z  m.p. (°C.)                             __________________________________________________________________________     H    H   H  H   H  CH.sub.3                                                                           CH.sub.3                                                                              CH                                               H    H   H  H   H  CH.sub.3                                                                           OCH.sub.3                                                                             CH 178-185°                               H    H   H  H   H  OCH.sub.3                                                                          OCH.sub.3                                                                             CH 197-210°                               H    H   H  H   H  CH.sub.3                                                                           CH.sub.3                                                                              N                                                H    H   H  H   H  CH.sub.3                                                                           OCH.sub.3                                                                             N                                                H    H   H  H   H  OCH.sub. 3                                                                         OCH.sub.3                                                                             N                                                H    H   H  H   H  CH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                    CH                                               H    H   H  H   H  CH.sub.3                                                                           CH(OCH.sub.3).sub.2                                                                   CH                                               H    H   H  H   H  CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                     CH                                               H    H   H  H   H  OCH.sub.3                                                                          NH.sub.2                                                                              CH                                               H    H   H  H   H  OCH.sub.3                                                                          NHCH.sub.3                                                                            CH                                               H    H   H  H   H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                                                   CH                                               H    H   H  H   H  Cl  OCH.sub.3                                                                             CH                                               H    H   H  H   H  CH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                    N                                                H    H   H  H   H  OCH.sub.3                                                                          N(CH.sub.3).sub.2                                                                     N                                                H    H   H  H   H  CH.sub.3                                                                           CH(OCH.sub.3).sub.2                                                                   N                                                H    H   H  H   H  OCH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                    N                                                H    CH.sub.3                                                                           H  H   H  CH.sub.3                                                                           OCH.sub.3                                                                             N                                                H    CH.sub.3                                                                           H  CH.sub.3                                                                           H  OCH.sub.3                                                                          OCH.sub.3                                                                             N                                                H    OCH.sub.3                                                                          H  CH.sub.3                                                                           H  CH.sub.3                                                                           CH(OCH.sub.3).sub.2                                                                   N                                                H    OCH.sub.3                                                                          H  H   H  CH.sub.3                                                                           CH(OCH.sub.3).sub.2                                                                   N                                                3-Cl H   H  H   H  CH.sub.3                                                                           OCH.sub.3                                                                             CH                                               4-Cl H   H  H   H  OCH.sub.3                                                                          OCH.sub.3                                                                             N                                                4-Cl H   H  H   H  CH.sub.3                                                                           OCH.sub.3                                                                             N                                                4-Cl CH.sub.3                                                                           H  CH.sub.3                                                                           H  CH.sub.3                                                                           CH.sub.3                                                                              CH                                               4-Cl OCH.sub.3                                                                          H  OCH.sub.3                                                                          H  OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                               4-Cl H   H  H   H  OCH.sub.3                                                                          OCH.sub.3                                                                             N                                                4-Cl H   CH.sub.3                                                                          H   H  OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                               5-Cl H   H  H   CH.sub.3                                                                          CH.sub.3                                                                           OCH.sub.3                                                                             CH                                               3-CH.sub.3                                                                          H   H  H   H  CH.sub.3                                                                           CH.sub.3                                                                              CH                                               5-CH.sub.3                                                                          H   H  H   H  OCH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                    N                                                4-CH.sub.3                                                                          H   H  H   H  CH.sub.3                                                                           CH(OCH.sub.3).sub.2                                                                   CH                                               4-CH.sub.3                                                                          H   H  H   H  CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                     N                                                4-CH.sub.3                                                                          H   H  H   H  OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                               4-CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3                                                                          OCH.sub.3                                                                          H  OCH.sub.3                                                                          CH.sub.3                                                                              CH                                               4-OCH.sub.3                                                                         H   H  H   CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3                                                                              N                                                3-OCH.sub.3                                                                         CH.sub.3                                                                           CH.sub.3                                                                          H   H  OCH.sub.3                                                                          OCH.sub.3                                                                             N                                                6-OCH.sub.3                                                                         H   H  H   H  OCH.sub.3                                                                          OCH.sub.3                                                                             N                                                6-OCH.sub.3                                                                         H   H  H   H  CH.sub.3                                                                           OCH.sub.3                                                                             CH                                               6-OCH.sub.3                                                                         H   H  H   H  CH.sub.3                                                                           CH.sub.3                                                                              CH                                               6-F  H   H  H   H  OCH.sub.3                                                                          OCH.sub.3                                                                             N                                                5-F  H   H  H   H  CH.sub.3                                                                           OCH.sub.3                                                                             N                                                3-F  H   H  H   H  CH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                    CH                                               3-F  H   H  H   H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                                                   CH                                               3-F  H   H  H   H  CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                     N                                                3-F  H   H  H   CH.sub.3                                                                          CH.sub.3                                                                           OCH.sub.3                                                                             CH                                               3-F  OCH.sub.3                                                                          CH.sub.3                                                                          OCH.sub.3                                                                          H  CH.sub.3                                                                           OCH.sub.3                                                                             N                                                __________________________________________________________________________

                                      TABLE V                                      __________________________________________________________________________      ##STR17##                                                                     R.sub.1                                                                             R.sub.7                                                                             R.sub.8                                                                             R.sub.17                                                                          X   Y      Z  m.p. (°C.)                              __________________________________________________________________________     H    H    H    H  CH.sub.3                                                                           CH.sub.3                                                                              CH                                                H    H    H    H  OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                H    H    H    H  CH.sub.3                                                                           CH.sub.3                                                                              N                                                 H    H    H    H  CH.sub.3                                                                           OCH.sub.3                                                                             N                                                 H    H    H    H  OCH.sub.3                                                                          OCH.sub.3                                                                             N                                                 H    H    H    H  CH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                    CH                                                H    H    H    H  CH.sub.3                                                                           CH(OCH.sub.3).sub.2                                                                   CH                                                H    H    H    H  OCH.sub.3                                                                          N(CH.sub.3).sub.2                                                                     N                                                 H    H    H    H  OCH.sub.3                                                                          NH.sub.2                                                                              CH                                                H    H    H    H  Cl  OCH.sub.3                                                                             CH                                                H    H    H    H  OCH.sub.3                                                                          NHCH.sub.3                                                                            CH                                                H    H    H    H  CH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                    N                                                 H    H    H    H  Cl  CH.sub.3                                                                              CH                                                H    H    H    H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                                                   N                                                 H    2'-CH.sub.3                                                                         H    H  CH.sub.3                                                                           CH.sub.3                                                                              CH                                                H    2'-CH.sub.3                                                                         6'-OCH.sub.3                                                                        H  CH.sub.3                                                                           OCH.sub.3                                                                             N                                                 H    2'-OCH.sub.3                                                                        H    H  OCH.sub.3                                                                          OCH.sub.3                                                                             N                                                 H    5'-CH.sub.3                                                                         H    H  OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                H    2'-OCH.sub.3                                                                        5'-CH.sub.3                                                                         H  CH.sub.3                                                                           CH.sub.3                                                                              CH                                                H    6'-CH.sub.3                                                                         H    H  OCH.sub.3                                                                          CH.sub.3                                                                              CH                                                H    H    H    CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3                                                                              CH                                                H    H    H    CH.sub.3                                                                          OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                H    2'-CH.sub.3                                                                         H    H  CH.sub.3                                                                           CH.sub.3                                                                              N                                                 H    H    H    H  OCH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                    N                                                 H    6'-CH.sub.3                                                                         H    H  CH.sub.3                                                                           CH.sub.3                                                                              CH                                                H    H    H    H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                                                   CH                                                4-F  H    H    H  CH.sub.3                                                                           CH.sub.3                                                                              N                                                 4-F  H    H    H  OCH.sub.3                                                                          CH.sub.3                                                                              N                                                 4-F  H    H    H  CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                     CH                                                4-F  H    H    H  Cl  OCH.sub.3                                                                             CH                                                4-F  H    H    CH.sub.3                                                                          OCH.sub.3                                                                          NH.sub.2                                                                              N                                                 4-F  H    H    H  CH.sub.3                                                                           OCH.sub.3                                                                             N                                                 5-Cl H    H    H  OCH.sub.3                                                                          CH.sub.3                                                                              CH                                                5-Cl H    H    H  CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                      CH                                                5-Cl H    H    H  OCH.sub.3                                                                          C.sub.2 H.sub.5                                                                       N                                                 5-Cl H    H    H  Cl  CH.sub.2 OCH.sub.3                                                                    N                                                 5-Cl H    H    H  OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                5-Cl H    H    CH.sub.3                                                                          CH.sub.3                                                                           OCH.sub.3                                                                             CH                                                3-CH.sub.3                                                                          H    H    H  OCH.sub.3                                                                          NHCH.sub.3                                                                            N                                                 3-CH.sub.3                                                                          H    H    H  CH.sub.3                                                                           C.sub.2 H.sub.5                                                                       N                                                 3-CH.sub.3                                                                          H    H    H  OCH.sub.3                                                                          CH.sub.3                                                                              CH                                                3-CH.sub.3                                                                          2'-CH.sub.3                                                                         H    H  CH.sub.3                                                                           CH.sub.3                                                                              CH                                                3-CH.sub.3                                                                          H    H    H  OCH.sub.3                                                                          CH.sub.3                                                                              N                                                 4-OCH.sub.3                                                                         H    H    H  CH.sub.3                                                                           OCH.sub.3                                                                             N                                                 4-OCH.sub.3                                                                         H    H    H  OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                4-OCH.sub.3                                                                         H    H    H  CH.sub.3                                                                           CH.sub.3                                                                              CH                                                4-OCH.sub.3                                                                         H    H    H  OCH.sub.3                                                                          OCH.sub.3                                                                             N                                                 __________________________________________________________________________

                                      TABLE VI                                     __________________________________________________________________________      ##STR18##                                                                     R.sub.1                                                                             R.sub.7                                                                             R.sub.8                                                                            R.sub.17                                                                          X   Y      Z  m.p. (°C.)                               __________________________________________________________________________     H    H    H   H  CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 H    H    H   H  CH.sub.3                                                                           OCH.sub.3                                                                             CH                                                 H    H    H   H  OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                 H    H    H   H  CH.sub.3                                                                           CH.sub.3                                                                              N                                                  H    H    H   H  CH.sub.3                                                                           OCH.sub.3                                                                             N                                                  H    H    H   H  OCH.sub.3                                                                          OCH.sub. 3                                                                            N                                                  H    H    H   H  CH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                    CH                                                 H    H    H   H  CH.sub.3                                                                           CH(OCH.sub.3).sub.2                                                                   CH                                                 H    H    H   H  OCH.sub.3                                                                          N(CH.sub.3).sub.2                                                                     N                                                  H    H    H   H  OCH.sub.3                                                                          NH.sub.2                                                                              CH                                                 H    H    H   H  Cl  OCH.sub.3                                                                             CH                                                 H    H    H   H  OCH.sub.3                                                                          NHCH.sub.3                                                                            CH                                                 H    H    H   H  CH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                    N                                                  H    H    H   H  Cl  CH.sub.3                                                                              CH                                                 H    H    H   H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                                                   N                                                  H    2'-OCH.sub.3                                                                        H   H  CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 H    2'-CH.sub.3                                                                         4'-CH.sub.3                                                                        H  CH.sub.3                                                                           OCH.sub.3                                                                             N                                                  H    4'-OCH.sub.3                                                                        H   H  CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 H    2'-CH.sub.3                                                                         H   H  OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                 H    4'-CH.sub.3                                                                         6'-CH.sub.3                                                                        H  OCH.sub.3                                                                          OCH.sub.3                                                                             N                                                  H    2'-CH.sub.3                                                                         H   H  OCH.sub.3                                                                          OCH.sub.3                                                                             N                                                  H    H    H   CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 H    H    H   CH.sub.3                                                                          OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                 H    2'-CH.sub.3                                                                         H   H  CH.sub.3                                                                           CH.sub.3                                                                              N                                                  H    H    H   H  OCH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                    N                                                  H    4'-CH.sub.3                                                                         6'-CH.sub.3                                                                        H  CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 H    H    H   H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                                                   CH                                                 5-F  H    H   H  CH.sub.3                                                                           CH.sub.3                                                                              N                                                  5-F  H    H   H  OCH.sub.3                                                                          CH.sub.3                                                                              N                                                  5-F  H    H   H  CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                     CH                                                 5-F  H    H   H  Cl  OCH.sub.3                                                                             CH                                                 5-F  H    H   CH.sub.3                                                                          OCH.sub.3                                                                          NH.sub.2                                                                              N                                                  5-F  H    H   H  CH.sub.3                                                                           OCH.sub.3                                                                             N                                                  3-Cl H    H   H  OCH.sub.3                                                                          CH.sub.3                                                                              CH                                                 3-Cl H    H   H  CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                      CH                                                 3-Cl H    H   H  OCH.sub.3                                                                          C.sub.2 H.sub.5                                                                       N                                                  3-Cl H    H   H  Cl  CH.sub.2 OCH.sub.3                                                                    N                                                  3-Cl H    H   H  OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                 3-Cl H    H   CH.sub.3                                                                          CH.sub.3                                                                           OCH.sub.3                                                                             CH                                                 4-CH.sub.3                                                                          H    H   H  OCH.sub.3                                                                          NHCH.sub.3                                                                            N                                                  4-CH.sub.3                                                                          H    H   H  CH.sub.3                                                                           C.sub.2 H.sub.5                                                                       N                                                  4-CH.sub.3                                                                          H    H   H  OCH.sub.3                                                                          CH.sub.3                                                                              CH                                                 4-CH.sub.3                                                                          H    H   H  CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 4-CH.sub.3                                                                          2'-CH.sub.3                                                                         H   H  OCH.sub.3                                                                          CH.sub. 3                                                                             N                                                  5-OCH.sub.3                                                                         H    H   H  CH.sub.3                                                                           OCH.sub.3                                                                             N                                                  5-OCH.sub.3                                                                         H    H   H  OCH.sub.3                                                                          OCH.sub.3                                                                             CH                                                 5-OCH.sub.3                                                                         H    H   H  CH.sub.3                                                                           CH.sub.3                                                                              CH                                                 5-OCH.sub.3                                                                         H    H   H  OCH.sub.3                                                                          OCH.sub.3                                                                             N                                                  __________________________________________________________________________

                                      TABLE VII                                    __________________________________________________________________________      ##STR19##                                                                     __________________________________________________________________________     R.sub.1                                                                             R.sub.9                                                                            R.sub.10                                                                           R.sub.17                                                                          X   Y       Z  m.p. (°C.)                               __________________________________________________________________________     H    H   H   H  CH.sub.3                                                                           CH.sub.3                                                                               CH 212-217° d                               H    H   H   H  CH.sub.3                                                                           OCH.sub.3                                                                              CH 178°                                     H    H   H   H  OCH.sub.3                                                                          OCH.sub.3                                                                              CH 178-179°                                 H    H   H   H  CH.sub.3                                                                           CH.sub.3                                                                               N                                                  H    H   H   H  CH.sub.3                                                                           OCH.sub.3                                                                              N                                                  H    H   H   H  OCH.sub.3                                                                          OCH.sub.3                                                                              N                                                  H    H   H   H  CH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                     CH                                                 H    H   H   H  CH.sub.3                                                                           CH(OCH.sub.3).sub.2                                                                    CH                                                 H    H   H   H  OCH.sub.3                                                                          N(CH.sub.3).sub.2                                                                      N                                                  H    H   H   H  OCH.sub.3                                                                          NH.sub.2                                                                               CH                                                 H    H   H   H  Cl  OCH.sub.3                                                                              CH                                                 H    H   H   H  OCH.sub.3                                                                          NHCH.sub.3                                                                             CH                                                 H    H   H   H  CH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                     N                                                  H    H   H   H  Cl  CH.sub.3                                                                               CH                                                 H    H   H   H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                                                    N                                                  H    3'-CH.sub.3                                                                        H   H  CH.sub.3                                                                           OCH.sub.3                                                                              CH                                                 H    5'-CH.sub.3                                                                        6'-CH.sub.3                                                                        H  CH.sub.3                                                                           OCH.sub.3                                                                              CH                                                 H    5'-CH.sub.3                                                                        H   H  CH.sub.3                                                                           CH.sub.3                                                                               CH                                                 H    6'-CH.sub.3                                                                        H   H  OCH.sub.3                                                                          OCH.sub.3                                                                              N                                                  H    3'-CH.sub.3                                                                        6'-CH.sub.3                                                                        H  OCH.sub.3                                                                          CH.sub.3                                                                               N                                                  H    3'-CH.sub.3                                                                        H   H  OCH.sub.3                                                                          OCH.sub.3                                                                              CH                                                 H    H   H   CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3                                                                               CH                                                 H    H   H   CH.sub.3                                                                          OCH.sub.3                                                                          OCH.sub.3                                                                              CH                                                 __________________________________________________________________________     R.sub.1                                                                             R.sub.2                                                                            R.sub.3                                                                            R.sub.17                                                                          X   Y       Z  m.p. (°C.)                               __________________________________________________________________________     H    6'-CH.sub.3                                                                        H   H  CH.sub.3                                                                           CH.sub.3                                                                               N                                                  H    H   H   H  OCH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                     N                                                  H    5'-CH.sub.3                                                                        6'-CH.sub.3                                                                        H  CH.sub.3                                                                           CH.sub.3                                                                               CH                                                 H    H   H   H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                                                    CH                                                 3-F  H   H   H  CH.sub.3                                                                           CH.sub.3                                                                               N                                                  3-F  H   H   H  OCH.sub.3                                                                          CH.sub.3                                                                               N                                                  3-F  H   H   H  CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                      CH                                                 3-F  H   H   H  Cl  OCH.sub.3                                                                              CH                                                 3-F  H   H   CH.sub.3                                                                          OCH.sub.3                                                                          NH.sub.2                                                                               N                                                  3-F  H   H   H  CH.sub.3                                                                           OCH.sub.3                                                                              N                                                  4-Cl H   H   H  OCH.sub.3                                                                          CH.sub.3                                                                               CH                                                 4-Cl H   H   H  CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                       CH                                                 4-Cl H   H   H  OCH.sub.3                                                                          C.sub.2 H.sub.5                                                                        N                                                  4-Cl H   H   H  Cl  CH.sub.2 OCH.sub.3                                                                     N                                                  4-Cl 6'-CH.sub.3                                                                        H   H  OCH.sub.3                                                                          OCH.sub.3                                                                              CH                                                 4-Cl H   H   CH.sub.3                                                                          CH.sub.3                                                                           OCH.sub.3                                                                              CH                                                 5-CH.sub.3                                                                          H   H   H  OCH.sub.3                                                                          NHCH.sub.3                                                                             N                                                  5-CH.sub.3                                                                          H   H   H  CH.sub.3                                                                           C.sub.2 H.sub.5                                                                        N                                                  5-CH.sub.3                                                                          H   H   H  OCH.sub.3                                                                          CH.sub. 3                                                                              CH                                                 5-CH.sub.3                                                                          H   H   H  CH.sub.3                                                                           CH.sub.3                                                                               CH                                                 5-CH.sub.3                                                                          H   H   H  OCH.sub.3                                                                          CH.sub.3                                                                               N                                                  6-OCH.sub.3                                                                         H   H   H  CH.sub.3                                                                           OCH.sub.3                                                                              N                                                  6-OCH.sub.3                                                                         H   H   H  OCH.sub.3                                                                          OCH.sub.3                                                                              CH                                                 6-OCH.sub.3                                                                         H   H   H  CH.sub.3                                                                           CH.sub.3                                                                               CH                                                 6-OCH.sub.3                                                                         H   H   H  OCH.sub.3                                                                          OCH.sub.3                                                                              N                                                  __________________________________________________________________________

                                      TABLE VIII                                   __________________________________________________________________________      ##STR20##                                                                     __________________________________________________________________________     R.sub.1                                                                             R.sub.11                                                                           R.sub.12                                                                           R.sub.17                                                                          X   Y       Z  m.p. (°C.)                               __________________________________________________________________________     H    H   H   H  CH.sub.3                                                                           CH.sub.3                                                                               CH                                                 H    H   H   H  CH.sub.3                                                                           OCH.sub.3                                                                              CH                                                 H    H   H   H  OCH.sub.3                                                                          OCH.sub.3                                                                              CH                                                 H    H   H   H  CH.sub.3                                                                           CH.sub.3                                                                               N                                                  H    H   H   H  CH.sub.3                                                                           OCH.sub.3                                                                              N                                                  H    H   H   H  OCH.sub.3                                                                          OCH.sub.3                                                                              N                                                  H    H   H   H  CH.sub.3                                                                           CH.sub. 2 OCH.sub.3                                                                    CH                                                 H    H   H   H  CH.sub.3                                                                           CH(OCH.sub.3).sub.2                                                                    CH                                                 H    H   H   H  OCH.sub.3                                                                          N(CH.sub.3).sub.2                                                                      N                                                  H    H   H   H  OCH.sub.3                                                                          NH.sub.2                                                                               CH                                                 H    H   H   H  Cl  OCH.sub.3                                                                              CH                                                 H    H   H   H  OCH.sub.3                                                                          NHCH.sub.3                                                                             CH                                                 H    H   H   H  CH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                     N                                                  H    H   H   H  Cl  CH.sub.3                                                                               CH                                                 H    H   H   H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                                                    N                                                  H    6'-CH.sub.3                                                                        H   H  CH.sub.3                                                                           OCH.sub.3                                                                              N                                                  H    4'-CH.sub.3                                                                        6'-CH.sub.3                                                                        H  OCH.sub.3                                                                          OCH.sub.3                                                                              CH                                                 H    6'-CH.sub.3                                                                        H   H  OCH.sub.3                                                                          OCH.sub.3                                                                              N                                                  H    5'-CH.sub.3                                                                        H   H  CH.sub.3                                                                           CH.sub.3                                                                               N                                                  H    4'-CH.sub.3                                                                        5'-CH.sub.3                                                                        H  OCH.sub.3                                                                          CH.sub.3                                                                               CH                                                 H    6'-CH.sub.3                                                                        H   H  CH.sub.3                                                                           OCH.sub.3                                                                              CH                                                 H    H   H   CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3                                                                               CH                                                 H    H   H   CH.sub.3                                                                          OCH.sub.3                                                                          OCH.sub.3                                                                              CH                                                 __________________________________________________________________________     R.sub.1                                                                             R.sub.2                                                                            R.sub.3                                                                            R.sub.17                                                                          X   Y       Z  m.p. (°C.)                               __________________________________________________________________________     H    6'-CH.sub.3                                                                        H   H  CH.sub.3                                                                           CH.sub.3                                                                               N                                                  H    H   H   H  OCH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                     N                                                  H    4'-CH.sub.3                                                                        H   H  CH.sub.3                                                                           CH.sub.3                                                                               CH                                                 H    H   H   H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                                                    CH                                                 6-F  H   H   H  CH.sub.3                                                                           CH.sub.3                                                                               N                                                  6-F  H   H   H  OCH.sub.3                                                                          CH.sub.3                                                                               N                                                  6-F  H   H   H  CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                      CH                                                 6-F  H   H   H  Cl  OCH.sub.3                                                                              CH                                                 6-F  H   H   CH.sub.3                                                                          OCH.sub.3                                                                          NH.sub.2                                                                               N                                                  6-F  H   H   H  CH.sub.3                                                                           OCH.sub.3                                                                              N                                                  5-Cl H   H   H  OCH.sub.3                                                                          CH.sub.3                                                                               CH                                                 5-Cl H   H   H  CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                       CH                                                 5-Cl 6'-CH.sub.3                                                                        H   H  OCH.sub.3                                                                          C.sub.2 H.sub.5                                                                        N                                                  5-Cl H   H   H  Cl  CH.sub.2 OCH.sub.3                                                                     N                                                  5-Cl H   H   H  OCH.sub.3                                                                          OCH.sub.3                                                                              CH                                                 5-Cl H   H   CH.sub.3                                                                          CH.sub.3                                                                           OCH.sub.3                                                                              CH                                                 3-CH.sub.3                                                                          H   H   H  OCH.sub.3                                                                          NHCH.sub.3                                                                             N                                                  3-CH.sub.3                                                                          H   H   H  CH.sub.3                                                                           C.sub.2 H.sub.5                                                                        N                                                  3-CH.sub.3                                                                          H   H   H  OCH.sub.3                                                                          CH.sub.3                                                                               CH                                                 3-CH.sub.3                                                                          H   H   H  CH.sub.3                                                                           CH.sub.3                                                                               CH                                                 3-CH.sub.3                                                                          H   H   H  OCH.sub.3                                                                          CH.sub.3                                                                               N                                                  4-OCH.sub.3                                                                         H   H   H  CH.sub.3                                                                           OCH.sub.3                                                                              N                                                  4-OCH.sub.3                                                                         H   H   H  OCH.sub.3                                                                          OCH.sub.3                                                                              CH                                                 4-OCH.sub.3                                                                         H   H   H  CH.sub.3                                                                           CH.sub.3                                                                               CH                                                 4-OCH.sub.3                                                                         H   H   H  OCH.sub.3                                                                          OCH.sub.3                                                                              N                                                  __________________________________________________________________________

                                      TABLE IX                                     __________________________________________________________________________      ##STR21##                                                                     R.sub.1                                                                             R.sub.11                                                                           R.sub.12                                                                           R.sub.17                                                                          X   Y       Z  m.p. (°C.)                               __________________________________________________________________________     H    CH.sub.3                                                                           CH.sub.3                                                                           H  CH.sub.3                                                                           CH.sub.3                                                                               CH                                                 H    CH.sub.3                                                                           CH.sub.3                                                                           H  CH.sub.3                                                                           OCH.sub.3                                                                              CH                                                 H    CH.sub.3                                                                           CH.sub.3                                                                           H  OCH.sub.3                                                                          OCH.sub.3                                                                              CH                                                 H    CH.sub.3                                                                           CH.sub.3                                                                           H  CH.sub.3                                                                           CH.sub.3                                                                               N                                                  H    CH.sub.3                                                                           CH.sub.3                                                                           H  CH.sub.3                                                                           OCH.sub.3                                                                              N                                                  H    CH.sub.3                                                                           CH.sub.3                                                                           H  OCH.sub.3                                                                          OCH.sub.3                                                                              N                                                  H    OCH.sub.3                                                                          OCH.sub.3                                                                          H  CH.sub.3                                                                           CH.sub.3                                                                               CH                                                 H    OCH.sub.3                                                                          OCH.sub.3                                                                          H  Cl  OCH.sub.3                                                                              CH                                                 H    OCH.sub.3                                                                          OCH.sub.3                                                                          H  OCH.sub.3                                                                          OCH.sub.3                                                                              CH                                                 H    OCH.sub.3                                                                          OCH.sub.3                                                                          H  CH.sub.3                                                                           CH.sub.3                                                                               N                                                  H    OCH.sub.3                                                                          OCH.sub.3                                                                          H  CH.sub.3                                                                           OCH.sub.3                                                                              N                                                  H    OCH.sub.3                                                                          OCH.sub.3                                                                          H  OCH.sub.3                                                                          OCH.sub.3                                                                              N                                                  H    OCH.sub.3                                                                          CH.sub.3                                                                           H  CH.sub.3                                                                           CH.sub.3                                                                               CH                                                 H    OCH.sub.3                                                                          CH.sub.3                                                                           H  CH.sub.3                                                                           OCH.sub.3                                                                              CH                                                 H    OCH.sub.3                                                                          CH.sub.3                                                                           H  OCH.sub.3                                                                          OCH.sub.3                                                                              CH                                                 H    OCH.sub.3                                                                          CH.sub.3                                                                           H  CH.sub.3                                                                           CH.sub.3                                                                               N                                                  H    OCH.sub.3                                                                          CH.sub.3                                                                           H  CH.sub.3                                                                           OCH.sub.3                                                                              N                                                  H    OCH.sub.3                                                                          CH.sub.3                                                                           H  OCH.sub.3                                                                          OCH.sub.3                                                                              N                                                  H    OCH.sub.3                                                                          CH.sub.3                                                                           H  CH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                     CH                                                 H    OCH.sub.3                                                                          CH.sub.3                                                                           H  CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                      CH                                                 H    OCH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3                                                                          OCH.sub.3                                                                          CH.sub.3                                                                               CH                                                 H    OCH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                           CH(OCH.sub.3).sub.2                                                                    CH                                                 H    OCH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3                                                                               CH                                                 3-Cl                                                                           H.sub.3                                                                             CH.sub.3                                                                           H   CH.sub.3                                                                          CH.sub.3                                                                           CH                                                         3-Cl CH.sub.3                                                                           CH.sub.3                                                                           H  CH.sub.3                                                                           OCH.sub.3                                                                              CH                                                 3-Cl CH.sub.3                                                                           CH.sub.3                                                                           H  OCH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                     CH                                                 4-Cl CH.sub.3                                                                           CH.sub.3                                                                           H  CH.sub.3                                                                           CH.sub.3                                                                               N                                                  5-Cl CH.sub.3                                                                           CH.sub.3                                                                           H  CH.sub.3                                                                           OCH.sub.3                                                                              N                                                  5-Cl CH.sub.3                                                                           CH.sub.3                                                                           H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                                                    N                                                  5-Cl OCH.sub.3                                                                          OCH.sub.3                                                                          H  CH.sub.3                                                                           OCH.sub.3                                                                              CH                                                 4-CH.sub.3                                                                          OCH.sub.3                                                                          OCH.sub.3                                                                          H  Cl  CH.sub.3                                                                               CH                                                 3-CH.sub.3                                                                          OCH.sub.3                                                                          OCH.sub.3                                                                          H  OCH.sub.3                                                                          OCH.sub.3                                                                              CH                                                 6-F  OCH.sub.3                                                                          OCH.sub.3                                                                          H  CH.sub.3                                                                           CH.sub.3                                                                               N                                                  5-OCH.sub.3                                                                         OCH.sub.3                                                                          OCH.sub.3                                                                          H  CH.sub.3                                                                           CH.sub.3                                                                               N                                                  H    OCH.sub.3                                                                          OCH.sub.3                                                                          H  OCH.sub.3                                                                          N(CH.sub.3).sub.2                                                                      N                                                  H    OCH.sub.3                                                                          CH.sub.3                                                                           H  CH.sub.3                                                                           NH.sub.2                                                                               CH                                                 H    OCH.sub.3                                                                          CH.sub.3                                                                           H  CH.sub.3                                                                           NHCH.sub.3                                                                             CH                                                 H    OCH.sub.3                                                                          CH.sub.3                                                                           H  OCH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                     CH                                                 H    OCH.sub.3                                                                          CH.sub.3                                                                           H  CH.sub.3                                                                           CH(OCH.sub.3).sub.2                                                                    N                                                  H    OCH.sub.3                                                                          CH.sub.3                                                                           H  CH.sub.3                                                                           NHCH.sub.3                                                                             N                                                  H    OCH.sub.3                                                                          CH.sub.3                                                                           H  OCH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                     N                                                  H    OCH.sub.3                                                                          CH.sub.3                                                                           H  CH.sub.3                                                                           CH(OCH.sub.3).sub.2                                                                    CH                                                 H    OCH.sub.3                                                                          CH.sub.3                                                                           H  CH.sub.3                                                                           N(CH.sub.3).sub.2                                                                      CH                                                 H    OCH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3                                                                          OCH.sub.3                                                                          OCH.sub.3                                                                              CH                                                 H    OCH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3                                                                               CH                                                 H    OCH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                           OCH.sub.3                                                                              CH                                                 __________________________________________________________________________

                  TABLE X                                                          ______________________________________                                          ##STR22##                                                                                                                    m.p.                            R.sub.1                                                                          R.sub.13 R.sub.14                                                                               R.sub.17                                                                             X    Y     Z (°C.)                             ______________________________________                                         H      CH.sub.3                                                                               CH.sub.3                                                                               H    CH.sub.3                                                                             CH.sub.3                                                                               CH                                   H      CH.sub.3                                                                               CH.sub.3                                                                               H    CH.sub.3                                                                             OCH.sub.3                                                                              CH                                   H      CH.sub.3                                                                               CH.sub.3                                                                               H    OCH.sub.3                                                                            OCH.sub.3                                                                              CH                                   H      CH.sub.3                                                                               CH.sub.3                                                                               H    CH.sub.3                                                                             CH.sub.3                                                                               N                                    H      CH.sub.3                                                                               CH.sub.3                                                                               H    CH.sub.3                                                                             OCH.sub.3                                                                              N                                    H      CH.sub.3                                                                               CH.sub.3                                                                               H    OCH.sub.3                                                                            OCH.sub.3                                                                              N                                    H      OCH.sub.3                                                                              CH.sub.3                                                                               H    CH.sub.3                                                                             CH.sub.3                                                                               CH                                   H      OCH.sub.3                                                                              CH.sub.3                                                                               H    CH.sub.3                                                                             OCH.sub.3                                                                              CH                                   H      OCH.sub.3                                                                              CH.sub.3                                                                               H    OCH.sub.3                                                                            OCH.sub.3                                                                              CH                                   H      OCH.sub.3                                                                              CH.sub.3                                                                               H    CH.sub.3                                                                             CH.sub.3                                                                               N                                    H      OCH.sub.3                                                                              CH.sub.3                                                                               H    CH.sub.3                                                                             OCH.sub.3                                                                              N                                    H      OCH.sub.3                                                                              CH.sub.3                                                                               H    OCH.sub.3                                                                            OCH.sub.3                                                                              N                                    H      OCH.sub.3                                                                              CH.sub.3                                                                               H    CH.sub.3                                                                             CH.sub.2 OCH.sub.3                                                                     CH                                   H      OCH.sub.3                                                                              OCH.sub.3                                                                              H    CH.sub.3                                                                             CH.sub.3                                                                               CH                                   H      OCH.sub.3                                                                              OCH.sub.3                                                                              H    OCH.sub.3                                                                            CH.sub.2 OCH.sub.3                                                                     CH                                   H      OCH.sub.3                                                                              OCH.sub.3                                                                              H    CH.sub.3                                                                             OCH.sub.3                                                                              N                                    H      OCH.sub.3                                                                              OCH.sub.3                                                                              H    OCH.sub.3                                                                            OCH.sub.3                                                                              N                                    H      OCH.sub.3                                                                              OCH.sub.3                                                                              H    Cl    OCH.sub.3                                                                              CH                                   H      OCH.sub.3                                                                              OCH.sub.3                                                                              H    OCH.sub.3                                                                            OCH.sub.3                                                                              CH                                   H      CH.sub.3                                                                               CH.sub.3                                                                               CH.sub.3                                                                            CH.sub.3                                                                             CH.sub.3                                                                               CH                                   H      CH.sub.3                                                                               OCH.sub.3                                                                              CH.sub.3                                                                            CH.sub.3                                                                             OCH.sub.3                                                                              CH                                   H      OCH.sub.3                                                                              OCH.sub.3                                                                              CH.sub.3                                                                            OCH.sub.3                                                                            CH.sub.3                                                                               N                                    H      CH.sub.3                                                                               CH.sub.3                                                                               CH.sub.3                                                                            OCH.sub.3                                                                            OCH.sub.3                                                                              N                                    5-CH.sub.3                                                                            CH.sub.3                                                                               CH.sub.3                                                                               H    CH.sub.3                                                                             CH.sub.3                                                                               CH                                   4-Cl   CH.sub.3                                                                               CH.sub.3                                                                               H    CH.sub.3                                                                             OCH.sub.3                                                                              CH                                   4-Cl   CH.sub.3                                                                               CH.sub.3                                                                               H    OCH.sub.3                                                                            OCH.sub.3                                                                              CH                                   4-Cl   CH.sub.3                                                                               CH.sub.3                                                                               H    CH.sub.3                                                                             CH.sub.3                                                                               N                                    6-Cl   CH.sub.3                                                                               CH.sub.3                                                                               H    CH.sub.3                                                                             OCH.sub.3                                                                              N                                    3-Cl   CH.sub.3                                                                               CH.sub.3                                                                               H    OCH.sub.3                                                                            OCH.sub.3                                                                              N                                    5-F    OCH.sub.3                                                                              CH.sub.3                                                                               H    CH.sub.3                                                                             CH.sub.3                                                                               CH                                   5-F    OCH.sub.3                                                                              CH.sub.3                                                                               H    CH.sub.3                                                                             OCH.sub.3                                                                              CH                                   5-F    OCH.sub.3                                                                              CH.sub.3                                                                               H    OCH.sub.3                                                                            OCH.sub.3                                                                              CH                                   3-CH.sub.3                                                                            OCH.sub.3                                                                              CH.sub.3                                                                               H    CH.sub.3                                                                             CH.sub.3                                                                               N                                    3-CH.sub.3                                                                            OCH.sub.3                                                                              CH.sub.3                                                                               H    CH.sub.3                                                                             OCH.sub.3                                                                              N                                    3-CH.sub.3                                                                            OCH.sub.3                                                                              CH.sub.3                                                                               H    OCH.sub.3                                                                            OCH.sub.3                                                                              N                                    4-OCH.sub.3                                                                           OCH.sub.3                                                                              CH.sub.3                                                                               H    CH.sub.3                                                                             CH.sub.2 OCH.sub.3                                                                     CH                                   4-OCH.sub.3                                                                           OCH.sub.3                                                                              OCH.sub.3                                                                              H    CH.sub.3                                                                             CH.sub.3                                                                               CH                                   4-OCH.sub.3                                                                           OCH.sub.3                                                                              OCH.sub.3                                                                              H    OCH.sub.3                                                                            CH.sub.2 OCH.sub.3                                                                     CH                                   3-F    OCH.sub.3                                                                              OCH.sub.3                                                                              H    CH.sub.3                                                                             OCH.sub.3                                                                              N                                    3-F    OCH.sub.3                                                                              OCH.sub.3                                                                              H    OCH.sub.3                                                                            OCH.sub.3                                                                              N                                    3-F    OCH.sub.3                                                                              OCH.sub.3                                                                              H    Cl    OCH.sub.3                                                                              CH                                   4-CH.sub.3                                                                            OCH.sub.3                                                                              OCH.sub.3                                                                              H    OCH.sub.3                                                                            OCH.sub.3                                                                              CH                                   4-CH.sub.3                                                                            CH.sub.3                                                                               CH.sub.3                                                                               CH.sub.3                                                                            CH.sub.3                                                                             CH.sub.3                                                                               CH                                   4-CH.sub.3                                                                            CH.sub.3                                                                               OCH.sub.3                                                                              CH.sub.3                                                                            CH.sub.3                                                                             OCH.sub.3                                                                              CH                                   H      OCH.sub.3                                                                              OCH.sub.3                                                                              CH.sub.3                                                                            OCH.sub.3                                                                            CH.sub.3                                                                               N                                    H      CH.sub.3                                                                               CH.sub.3                                                                               CH.sub.3                                                                            OCH.sub.3                                                                            OCH.sub.3                                                                              N                                    ______________________________________                                    

FORMULATIONS

Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:

                  TABLE XI                                                         ______________________________________                                                     Weight Percent*                                                                Active  Inert                                                                  Ingredient                                                                             Diluent(s)                                                                               Surfactant(s)                                    ______________________________________                                         Wettable Powders                                                                             20-90      0-74     1-10                                         Oil Suspensions,                                                                              3-50     40-95     0-15                                         Emulsions, Solutions,                                                          (including Emulsifiable                                                        Concentrates)                                                                  Aqueous Suspension                                                                           10-50     40-84     1-20                                         Dusts          1-25     70-99     0-5                                          Granules and Pellets                                                                         0.1-95      5-99.9  0-15                                         High Strength 90-99      0-10     0-2                                          Compositions                                                                   ______________________________________                                          *Active ingredient plus at least one of a Surfactant or a Diluent equals       100 weight percent.                                                      

Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, N.J., but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0° C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, etc.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.

Further information regarding the art of formulation may be found in the following references:

G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwise indicated.

EXAMPLE 4

    ______________________________________                                         Wettable Powder                                                                ______________________________________                                         N--[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-                                                      80%                                              (2-pyridinyl)benzenesulfonamide                                                sodium alkylnaphthalenesulfonate                                                                              2%                                              sodium ligninsulfonate         2%                                              synthetic amorphous silica     3%                                              kaolinite                     13%                                              ______________________________________                                    

The ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, reblended, and packaged.

EXAMPLE 5

    ______________________________________                                         Wettable Powder                                                                ______________________________________                                         N--[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-                                                          50%                                                (2-pyridinyl)benzenesulfonamide                                                sodium alkylnaphthalenesulfonate                                                                            2%                                                low viscosity methyl cellulose                                                                              2%                                                diatomaceous earth          46%                                                ______________________________________                                    

The ingredients are blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in diameter. The product is reblended before packaging.

EXAMPLE 6

    ______________________________________                                         Granule                                                                        ______________________________________                                         Wettable Powder of Example 5                                                                           5%                                                     attapulgite granules   95%                                                     (U.S.S. 20-40 mesh; 0.84-0.42 mm)                                              ______________________________________                                    

A slurry of wettable powder containing ≈25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.

EXAMPLE 7

    ______________________________________                                         Extruded Pellet                                                                ______________________________________                                         N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                          25%                                               (2-pyridinyl)benzenesulfonamide                                                anhydrous sodium sulfate     10%                                               crude calcium ligninsulfonate                                                                                5%                                               sodium alkylnaphthalenesulfonate                                                                             1%                                               calcium/magnesium bentonite  59%                                               ______________________________________                                    

The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled.

EXAMPLE 8

    ______________________________________                                         Oil Suspension                                                                 ______________________________________                                         N--[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-                                                      25%                                              (2-pyridinyl)benzenesulfonamide                                                polyoxyethylene sorbitol hexaoleate                                                                           5%                                              highly aliphatic hydrocarbon oil                                                                             70%                                              ______________________________________                                    

The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.

EXAMPLE 9

    ______________________________________                                         Wettable Powder                                                                ______________________________________                                         N--[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-                                                      20%                                              (2-pyridinyl)benzenesulfonamide                                                sodium alkylnaphthalenesulfonate                                                                             4%                                               sodium ligninsulfonate        4%                                               low viscosity methyl cellulose                                                                               3%                                               attapulgite                   69%                                              ______________________________________                                    

The ingredients are thoroughly blended. After grinding in a hammer-mill to produce particles essentially all below 100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.

EXAMPLE 10

    ______________________________________                                         Low Strength Granule                                                           ______________________________________                                         N--[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-                                                           1%                                                (2-pyridinyl)benzenesulfonamide                                                N,N--dimethylformamide       9%                                                attapulgite granules        90%                                                (U.S.S. 20-40 sieve)                                                           ______________________________________                                    

The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged.

EXAMPLE 11

    ______________________________________                                         Aqueous Suspension                                                             ______________________________________                                         N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                          40%                                               (2-pyridinyl)benzenesulfonamide                                                polyacrylic acid thickener  0.3%                                               dodecylphenol polyethylene glycol ether                                                                    0.5%                                               disodium phosphate            1%                                               monosodium phosphate        0.5%                                               polyvinyl alcohol           1.0%                                               water                       56.7%                                              ______________________________________                                    

The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.

EXAMPLE 12

    ______________________________________                                         Solution                                                                       ______________________________________                                         N--[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-                                                       5%                                              (2-pyridinyl)benzenesulfonamide                                                water                         95%                                              ______________________________________                                    

The salt is added directly to the water with stirring to produce the solution, which may then be packaged for use.

EXAMPLE 13

    ______________________________________                                         Low Strength Granule                                                           ______________________________________                                         N--[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-                                                        0.1%                                             2-(2-pyridinyl)benzenesulfonamide                                              attapulgite granules         99.9%                                             (U.S.S. 20-40 mesh)                                                            ______________________________________                                    

The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double-cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.

EXAMPLE 14

    ______________________________________                                         Granule                                                                        ______________________________________                                         N--[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-                                                          80%                                                (2-pyridinyl)benzenesulfonamide                                                wetting agent                1%                                                crude ligninsulfonate salt (containing                                                                     10%                                                5-20% of the natural sugars)                                                   attapulgite clay             9%                                                ______________________________________                                    

The ingredients ae blended and milled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and packaged for use.

EXAMPLE 15

    ______________________________________                                         High Strength Concentrate                                                      ______________________________________                                         N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                           99%                                              (2-pyridinyl)benzenesulfonamide                                                silica aerogel               0.5%                                              synthetic amorphous silica   0.5%                                              ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.

EXAMPLE 16

    ______________________________________                                         Wettable Powder                                                                ______________________________________                                         N--[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-                                                       90%                                             (2-pyridinyl)benzenesulfonamide                                                dioctyl sodium sulfosuccinate 0.1%                                             synthetic fine silica         9.9%                                             ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce particles essentially all below 100 microns. The material is sifted through a U.S.S. No. 50 screen and then packaged.

EXAMPLE 17

    ______________________________________                                         Wettable Powder                                                                ______________________________________                                         N--[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-                                                      40%                                              (2-pyridinyl)benzenesulfonamide                                                sodium ligninsulfonate        20%                                              montmorillonite clay          40%                                              ______________________________________                                    

The ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in size. The material is reblended and then packaged.

EXAMPLE 18

    ______________________________________                                         Oil Suspension                                                                 ______________________________________                                         N--[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-                                                          35%                                                (2-pyridinyl)benzenesulfonamide                                                blend of polyalcohol carboxylic                                                                             6%                                                esters and oil soluble petroleum                                               sulfonates                                                                     xylene                      59%                                                ______________________________________                                    

The ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water.

EXAMPLE 19

    ______________________________________                                         Dust                                                                           ______________________________________                                         N--[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-                                                      10%                                              (2-pyridinyl)benzenesulfonamide                                                attapulgite                   10%                                              Pyrophyllite                  80%                                              ______________________________________                                    

The active ingredient is blended with attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns. The ground concentrate is then blended with powdered pyrophyllite until homogeneous.

EXAMPLE 20

    ______________________________________                                         Emulsifiable Concentrate                                                       ______________________________________                                         N--[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                          20%                                               (2-pyridinyl)benzenesulfonamide                                                chlorobenzene                74%                                               sorbitan monostearate and polyoxyethylene                                                                    6%                                               condensates thereof                                                            ______________________________________                                    

The ingredients are combined and stirred to produce a solution which can be emulsified in water for application.

UTILITY

The compounds of the present invention are highly active herbicides. They can be used for broad-spectrum pre- and/or post-emergence weed control in areas where complete control of all vegetation is desired, such as around fuel storage tanks, ammunition depots, industrial storage areas, parking lots, drive-in theaters, around billboards, highway and railroad structures. Alternatively, the subject compounds are useful for plant growth modification, particularly in retarding the growth of undesired vegetation.

Rates of application for the compounds of this invention are ordinarily determined by a number of factors, including their use as either herbicides or plant growth modifiers, the types of weeds to be controlled, weather and climate, the formulation to be used, the mode of application, amount of foliage present, etc. In general terms, the subject compounds should be applied at levels of around 0.001 to 5 kg/ha, lower rates being preferred for lighter soils and/or those having a low organic matter content, for situations where only short-term persistence is required, or for plant growth modification.

The compounds of the invention may be used in combination with any other commercial herbicide, examples of which are those of the triazine, triazole, uracil, urea, amide, diphenylether, carbamate and bipyridylium types.

The herbicidal and plant growth modifying properties of the subject compounds were discovered in a number of greenhouse tests, the results of which may be seen in the following examples. ##STR23##

TEST A

Seeds of crabgrass (Digitaria, spp.), barnyard-grass (Echinochloa crusgalli), wild oats (Avena fatua), sicklepod (Cassia obtusifolia), morningglory (Ipomoea spp.), cocklebur (Xanthium pensylvanicum), sorghum, corn, soybean, sugar beet, rice, wheat, and purple nutsedge (Cyperus rotundus) tubers were planted and treated pre-emergence with the test chemicals dissolved in a non-phytotoxic solvent. At the same time, these crop and weed species, along with cotton and bush bean, were treated with a soil/foliage application. At the time of treatment, the plants ranged in height from 2 to 18 cm. Treated plants and controls were maintained in a greenhouse for sixteen days, after which all species were compared to controls and visually rated for response to treatment. The ratings, summarized in Table A, are based on a numerical scale extending from O=no injury, to 10=complete kill. The accompanying descriptive symbols have the following meanings:

C=chlorosis/necrosis;

E=emergence inhibition;

G=growth retardation;

H=formative effect; and

6Y=abscised buds or flowers.

                  TABLE A                                                          ______________________________________                                                    Cmpd. 1   Cmpd. 2  Cmpd. 3 Cmpd. 4                                  Rate kg/ha 0.05      0.05     0.05    0.05                                     ______________________________________                                         POST-EMERGENCE                                                                 Bush bean  4C,9G,6Y  4H,6Y    6C,9G,6Y                                                                               9C                                       Cotton     4C,9G     5C,7H    5C,9G   4C,9G                                    Morningglory                                                                              9C        4C,8H    5C,9G   10C                                      Cocklebur  9C        4C,8H    4C,9G   10C                                      Sicklepod  5C,7H     2C       3C,9G   9C                                       Nutsedge   2C,9G     3C,8G    2C,9G   6C,9G                                    Crabgrass  3C,8G     2C,4H    2C,8H   6C,9G                                    Barnyardgrass                                                                             3C,9H     3C,8H    5C,9H   9C                                       Wild Oats  3C,9G     3C,8H    2C,9G   9C                                       Wheat      2C,9G     2C,3H    2C,7G   9C                                       Corn       3C,9G     4C,9H    3C,9H   10C                                      Soybean    5C,9G     3C,9G    5C,9G   9C                                       Rice       5C,9G     6C,9G    5C,9G   6C,9G                                    Sorghum    3C,9H     5C,9H    2C,9H   6C,9G                                    Sugar beet 4C,8G     2C,4G    2C,9G   9C                                       PRE-EMERGENCE                                                                  Morningglory                                                                              9C        2C,6H    9C      3C,9H                                    Cocklebur  9H        5H,2C    9H      --                                       Sicklepod  9C        3H       2C,9G   2C,9G                                    Nutsedge   3G        0        10E     10E                                      Crabgrass  1C,2H     4G       2C,5G   3C,7G                                    Barnyardgrass                                                                             5C,9H     2C,4G    4C,9H   3C,9H                                    Wild Oats  5C,9G     2C,5G    2C,9G   3C,9H                                    Wheat      3C,9G     2C,3G    2C,9G   3C,9H                                    Corn       3C,9G     3C,5G    3C,9H   10E                                      Soybean    4C,7H     2C       3C,9H   9H                                       Rice       5C,9H     3C,5G    10E     10E                                      Sorghum    5C,9H     3C,7H    5C,9H   5C,9H                                    Sugar beet 5C,9G     3C,5H    9G      10E                                      ______________________________________                                    

TEST B

Two plastic bulb pans were filled with fertilized and limed Woodstown sandy loam. One pan was planted with corn, sorghum, Kentucky bluegrass and several grass weeds. The other pan was planted with cotton, soybeans, purple nutsedge (Cyperus rotundus), and several broadleaf weeds. The following grass and broadleaf weeds were planted: crabgrass (Digitaria sanguinalis), barnyardgrass (Echinochloa crusgalli), wild oats (Avena fatua), johnsongrass (Sorghum halepense), dallisgrass (Paspalum dilatatum), giant foxtail (Setaria faberii), cheatgrass (Bromus secalinus), mustard (Brassica arvensis), cocklebur (Xanthium pensylvanicum), morningglory (Ipomoea hederacea), sicklepod (Cassia obtusifolia), teaweed (Sida spinosa), velvetleaf (Abutilon theophrasti), and jimsonweed (Datura stramonium). A 12.5 cm diameter plastic pot was also filled with prepared soil and planted with rice and wheat. Another 12.5 cm pot was planted with sugar beets. The above four containers were treated pre-emergence with one of the test compounds from within the scope of the invention.

Twenty-eight days after treatment, the plants were evaluated and visually rated for response to the chemical treatments utilizing the rating system described previously for Test A. The data are summarized in Table B.

                  TABLE B                                                          ______________________________________                                         PRE-EMERGENCE ON                                                               WOODSTOWN SANDY LOAM                                                                          Compound 1                                                      Rate kg/ha       0.03        0.125                                             ______________________________________                                         Crabgrass        0           3G                                                Barnyardgrass    7G          9G                                                Sorghum          9G          10C                                               Wild Oats        5G          7G                                                Johnsongrass     7G          9G                                                Dallisgrass      6G          8G                                                Giant foxtail    3G          8G                                                Ky. bluegrass    6G          9G                                                Cheatgrass       8G          9G                                                Sugar beets      6G          8G                                                Corn             6G,5H       10C                                               Mustard          9G          9G                                                Cocklebur        7G          9G                                                Pigweed          --          --                                                Nutsedge         5G          6G                                                Cotton           3G          6G                                                Morningglory     6G          7G                                                Sicklepod        3G          7G                                                Teaweed          4G          7G                                                Velvetleaf       6G          8G                                                Jimsonweed       6G          9G                                                Soybean          4G,3C       7G,7H                                             Rice             8G          10C                                               Wheat            2G          6G                                                ______________________________________                                    

TEST C

The test chemical, dissolved in a non-phytotoxic solvent, was applied in an overall spray to the foliage and surrounding soil of selected plant species. One day after treatment, plants were checked for rapid burn injury. Approximately fourteen days after treatment all species were visually compared to untreated controls and rated for response to treatment. The rating system was as described previously for Test A. The data are presented in Table C.

All plant species were seeded in Woodstown sandy loam soil and grown in a greenhouse. The following species were grown in soil contained in plastic pots (25 cm diameter by 13 cm deep): soybeans, cotton, alfalfa, corn, rice, wheat, sorghum, velvetleaf (Abutilon theophrasti), sesbania (Sesbania exaltata), sicklepod (Cassia obtusifolia), morningglory (Ipomoea hederacea), jimsonweed (Datura stramonium), cocklebur (Xanthium pensylvanicum), crabgrass (Digitaria spp.), nutsedge (Cyperus esculentus), barnyardgrass (Echinochloa crusgalli), giant foxtail (Setaria faberil), bindweed (Convolvulus arvensis) and wild oats (Avena fatua). The following species were grown in soil in a paper cup (12 cm diameter by 13 cm deep); sunflower, sugar beets, and rape. All plants were sprayed approximately 14 days after planting.

The results of this test demonstrate the herbicidal activity of the test compound when applied as a soil/foliage treatment. It may also be seen that the treatments retard the growth of several plant species.

                  TABLE C                                                          ______________________________________                                         Over-the-Top Soil/Foliage Treatment                                                         Compound 4                                                        Rate kg/ha     0.25      0.063     0.016                                       ______________________________________                                         Soybeans       9C        10C       10C                                         Velvetleaf     7G        9G        10C                                         Sesbania       6G        9G        10C                                         Sicklepod      4C,6G     8G        9G                                          Cotton         9G        9G        9C                                          Morningglory   3G,4C     6G,6C     5C,7G                                       Alfalfa        8G        9C        10C                                         Jimsonweed     9G        10C       10C                                         Cocklebur      8G        9G        10C                                         Corn           3C,7G     6G,7C     10C                                         Crabgrass      7G        9G        9G                                          Rice           3C,4G     6C,3G     5G,4C                                       Nutsedge       6C,5G     7G        8G                                          Barnyardgrass  6G,6C     7G,6C     8G,4C                                       Wheat          7G        8G        8G                                          Giant foxtail  9G        10C       10C                                         Wild Oats      6G,4C     7G,7C     8G,7C                                       Sorghum        8G        8G        10C                                         Sunflower      10C       10C       10C                                         Rape           8G        10C       10C                                         Johnsongrass   7G        9G        10C                                         Sugar beets    9G        10C       10C                                         Bindweed       7G        8G        10C                                         ______________________________________                                     

What is claimed is:
 1. A compound of the formula: ##STR24## R₁ is H, F, Cl, CH₃ or OCH₃ ; R₅, R₉, R₁₀, R₁₁, R₁₂ and R₁₇ are independently H or CH₃ ;R₇, R₈, R₄ and R₆ are independently H, CH₃ or OCH₃ ; X is CH₃, OCH₃ or Cl; Y is CH₃, C₂ H₅, CH₂ OCH₃, OCH₃, OC₂ H₅, CH(OCH₃)₂ NH₂, NHCH₃ or N(CH₃)₂ ; Z is CH provided that when X is Cl, then Y is OCH₃, OC₂ H₅, NH₂, NHCH₃ or N(CH₃)₂ and when R₁ is CH₃, it is in the 3-, 4- or 5-position of the benzene ring;and their agriculturally suitable salts.
 2. Compounds of claim 1 where R₁ and R₁₇ are H and Y is CH₃, OCH₃, CH₂ OCH₃ or N(CH₃)₂.
 3. Compounds of claim 2 whereQ is ##STR25##
 4. Compounds of claim 2 whereQ is ##STR26##
 5. Compounds of claim 2 whereQ is ##STR27##
 6. The compound of claim 1 which is N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-(2-pyrimidinyl)benzenesulfonamide.
 7. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 1 and at least one of the following: surfactant, solid or liquid inert diluent.
 8. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 2 and at least one of the following: surfactant, solid or liquid inert diluent.
 9. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 1. 10. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 2. 